CN1919838A - Alpha-cyano-N-benzylpyrazoamide compound, preparation method and pest control agent thereof as active component - Google Patents
Alpha-cyano-N-benzylpyrazoamide compound, preparation method and pest control agent thereof as active component Download PDFInfo
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Abstract
The invention discloses an alpha-cyano-N-benzyl pyrazole amide compound and preparing method and pest prevention agent, which is characterized by the following: using organic solvent to react pyrazole formyl chloride and alpha-cyano benzylamine under -10-60 deg.c with general formula as (I); separating (I); adopting the compound or its acid salt as active to prepare pest prevention agent.
Description
Technical field
The invention belongs to pesticide field, relate to the alpha-cyano-N-benzyl pyrazole amide compound, the invention still further relates to the preparation method of this compound and be the pest control agent of activeconstituents with it.
Background technology
Heterogeneous ring compound occupies crucial status in the research and development of agricultural chemicals, especially nitrogen-containing heterocycle compound existingly much is used as agricultural chemicals and develops, and in field widespread uses such as agricultural and gardening, sterilant, weedicide are wherein not only arranged, and insecticidal/acaricidal agent is efficiently arranged.Wherein, the pyrazole amide derivatives of some N-replacement is also successfully developed as insecticidal/acaricidal agent.
US 4,950, and 668 disclose tebufenpyrad N-benzyl pyrazole-5-amide derivatives such as (tebufenpyrad) has desinsection and acaricidal activity.
(tebufenpyrad: tebufenpyrad)
US 5,039, and 693 disclose azoles insect amide (tolfenpyrad) etc. has N-benzyl pyrazole-5-amide derivatives that phenoxy group replaces and have pesticide and miticide actility.
(azoles insect amide: tolfenpyrad)
WO 02/083647 discloses the pyrazole amide derivatives that following compound (IV) etc. has xenyl and has had sterilization, desinsection and acaricidal activity.
But, also do not have reported in literature alpha-cyano-N-benzyl pyrazole acidamide compound and the application aspect sterilant, sterilant, miticide thereof.
Summary of the invention
The purpose of this invention is to provide a kind of have high reactivity, low consumption and the good alpha-cyano-N-benzyl pyrazole acidamide compound of security.
Another object of the present invention provides the preparation method of above-claimed cpd.
The present invention also a purpose to provide with the above-claimed cpd be the pest control agent of activeconstituents.
The objective of the invention is to realize by following measures:
The present invention relates to pyrazol acid amide compounds by general formula (I) expression:
Wherein:
R
1Expression C
1-C
5Alkyl;
R
2Expression C
1-C
5Alkyl or C
1-C
5Haloalkyl;
R
3Expression hydrogen or C
1-C
5Alkyl;
R
4Expression hydrogen, halogen, cyano group, C
1-C
5Alkyl, C
1-C
5Alkoxyl group, C
1-C
5Haloalkyl, aryl, substituted aryl, aryloxy or substituted aryloxy;
X represents hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base.
Pyrazol acid amide compounds:
Of the present invention by in the represented alpha-cyano-N-benzyl pyrazole acidamide compound of general formula (I), described substituent R
1Represent C straight chain or side chain
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl.Wherein, preferable methyl is as described substituent R
1
Described substituent R
2Represent C straight chain or side chain
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl or cyclopropyl; C straight chain or side chain
1-C
5Haloalkyl, as methyl fluoride, chloromethyl, brooethyl, difluoromethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl, 1-(trifluoromethyl) ethyl etc.Wherein, preferred C
1-C
3Alkyl, preferred especially ethyl is as described substituent R
2
Described substituent R
3Expression hydrogen; C straight chain or side chain
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl or cyclopropyl.Wherein, preferred hydrogen is as described substituent R
3
Described substituent R
4Expression hydrogen; Halogen is as fluorine, chlorine, bromine or iodine; Cyano group; C straight chain or side chain
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl or cyclopropyl; C straight chain or side chain
1-C
5Alkoxyl group is as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy or ring propoxy-base; C straight chain or side chain
1-C
5Haloalkyl, as methyl fluoride, chloromethyl, brooethyl, difluoromethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl, 1-(trifluoromethyl) ethyl etc.; Aryl is as phenyl, halogenophenyl, p-methylphenyl, o-tolyl, a tolyl or p-trifluoromethyl phenyl; Aryloxy is as phenoxy group, halogenated phenoxy, to tolyloxy, oxy-o-cresyl, a tolyloxy or 4-(trifluoromethyl)phenoxy.
Described substituent X is represented hydrogen; Halogen is as fluorine, chlorine, bromine or iodine; C
1-C
3Alkyl is as methyl, ethyl, n-propyl or sec.-propyl; C
1-C
3Alkoxyl group is as methoxyl group, oxyethyl group, positive propoxy or isopropoxy; Nitro; Cyano group; Thiocyanogen; Trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base.Wherein, preferred hydrogen and halogen are as described substituent X.
The synthetic method of described pyrazol acid amide compounds:
Alpha-cyano-N-benzyl pyrazole acidamide compound by general formula (I) expression of the present invention is a class novel cpd, and described compound can make according to for example following reaction process is synthetic:
Wherein, substituent R
1, R
2, R
3, R
4Identical with X with the definition in the general formula (I).
According to above-mentioned reaction equation, under the situation that has alkali or alkali-free to exist, make the reaction of pyrazol formyl chloride (III) and alpha-cyano benzylamine (IV), described reaction is preferably with an organic solvent carried out under-10 to 60 ℃ of conditions, and its preferable reaction temperature is 0 to 30 ℃.
Described organic solvent is that reaction is not had directly any inert solvent of influence, comprise aromatic hydrocarbons (as benzene, toluene and dimethylbenzene), ketone (as acetone, methylethylketone and mibk), halohydrocarbon (as chloroform, methylene dichloride and ethylene dichloride), ester class (as methyl acetate and ethyl acetate) and polar solvent (as tetrahydrofuran (THF), acetonitrile, diox, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide or pyridine).
Described alkali comprises alkalimetal hydride (as sodium hydride), alkali metal hydroxide (as sodium hydroxide and potassium hydroxide), alkaline carbonate (as yellow soda ash and salt of wormwood), alkali metal hydrocarbonate (as sodium bicarbonate and saleratus), organic bases (as pyridine and triethylamine).
For the target compound shown in the separate type after reaction (I), under the situation of using water-soluble solvent, decompression earlier removes solvent, in resistates, add water, use water-fast aromatic hydrocarbons (as benzene, toluene and dimethylbenzene) then, halohydrocarbon (as chloroform, methylene dichloride and ethylene dichloride), or the described resistates of ester class (as ethyl acetate) solvent extraction, and with the resulting extraction liquid of saturated common salt water washing, with anhydrous sodium sulphate or anhydrous magnesium sulfate organic phase is carried out drying again, decompression removes solvent then.When using water-immiscible solvent, then in the gained reaction mixture, add water and saturated common salt water washing successively, precipitation reduces pressure after the organic phase drying.After boiling off solvent, can carry out purification processes to the resistates that obtains by methods such as recrystallization and column chromatographies, thereby obtain target compound by general formula (I) expression.
The pyrazol formyl chloride by general formula (III) expression as intermediate can adopt currently known methods, for example at Bull.Soc.Chim.France, and 293 (1996) and US 4,950, the method described in 668 is synthesized and is made.
As the alpha-cyano benzylamine compound by general formula (IV) expression of intermediate, can adopt corresponding aroma aldehyde or aromatic ketone (V) to make via for example Strecker method is synthetic.
Wherein, substituent R
3And R
4Identical with the definition in the general formula (I).
According to above-mentioned reaction equation, preferably with an organic solvent under 0 to 100 ℃, make aromatic aldehyde or aromatic ketone (V) carry out the Strecker reaction, make alpha-cyano benzylamine (IV), preferred 20 to 50 ℃ of its temperature of reaction.
Described organic solvent is that reaction is not had directly any inert solvent of influence, comprises aromatic hydrocarbons, as benzene, toluene and dimethylbenzene; Halohydrocarbon is as chloroform, methylene dichloride and ethylene dichloride; Water; And polar solvent, as tetrahydrofuran (THF), methyl alcohol, acetonitrile, diox, N, dinethylformamide, N-Methyl pyrrolidone and methyl-sulphoxide.
Target compound for shown in the separate type after reaction (IV) can extract reaction mixture with solvent, and organic phase saturated common salt water washing removes solvent under reduced pressure then.
Can pass through ordinary method, at-5 to 50 ℃, under preferred 0 to 25 ℃, alpha-cyano benzylamine (IV) and organic acid or mineral acid be reacted, the hydrochlorate of synthetic alpha-cyano benzylamine.
Described organic acid comprises carboxylic acid, as acetate, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, toxilic acid, phenylformic acid and phthalic acid; Sulfonic acid, as methylsulfonic acid, 1,3-third disulfonic acid, tosic acid or Witco 1298 Soft Acid.Described mineral acid comprises hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
Described solvent is that reaction is not had directly any inert solvent of influence, comprises aromatic hydrocarbons, as benzene, toluene and dimethylbenzene; Halohydrocarbon is as chloroform, methylene dichloride and ethylene dichloride; Water; The ester class is as methyl acetate and ethyl acetate; And polar solvent, as tetrahydrofuran (THF), acetonitrile, diox, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide.
After the reaction, can reduce pressure and slough partial solvent, filter and collect the crystallization of formation, thereby obtain the organic acid salt or the inorganic acid salt of described alpha-cyano benzylamine.
Pest control agent:
The compounds of this invention by general formula (I) expression has good control activity to phytopathogen and insect, thereby compound of the present invention can be used as the activeconstituents of sterilant, miticide or the sterilant of agricultural, gardening aspect.Described phytopathogen such as rice Pyricularia grisea, all kinds of plant powdery mildew germ and oidium germ etc.Described insect has homoptera pest such as leafhopper, plant hopper, aphid, aleyrodid etc.; Hemiptera insect such as stinkbug class, stinkbug etc.; Lepidoptera pest such as bollworm, beet armyworm, small cabbage moth, cabbage caterpillar, Cnaphalocrocis medinali(rice leaf roller) and striped rice borer etc.; Diptera pest such as housefly and culex pipiens pollens etc.; Insect such as Orthoptera and Coleoptera, and acarina such as Tetranychus urticae, carmine spider mite and citrus red mite etc.Certainly, compound of the present invention germ, insect and the evil mite that can prevent and treat is not limited to above-mentioned scope of giving an example.
When by the compound of the present invention of general formula (I) expression during as the sterilant in agricultural, gardening and flower culture field, miticide or sterilant, can use separately, or adopt this area inert ingredient commonly used to be processed into missible oil, pulvis, wettable powder, suspension agent, granule, water-dispersible granules and aqueous emulsion etc.
Inert ingredient commonly used comprises solid carrier, as clay, kaolin, talcum, diatomite, silica, lime carbonate, polynite, wilkinite, starch and Sudan Gum-arabic; Liquid vehicle is as water; Organic solvent such as toluene, dimethylbenzene, hexanaphthene, methyl alcohol, butanols, ethylene glycol, acetone, dimethyl formamide, acetonitrile, methyl-sulphoxide, animal and plant oil and lipid acid; Tensio-active agent such as emulsifying agent and dispersion agent commonly used comprise anion surfactant, cats product, nonionogenic tenside and amphoterics; Other auxiliary agent is as wetting agent, thickening material and disintegrating agent etc.
By the compound of the present invention of general formula (I) expression during as the activeconstituents in sterilant, miticide or the sterilant, content in described sterilant, miticide or sterilant can be selected in 0.1% to 99.5% scope, and can determine suitable active component content according to dosage form and application process.Usually, contain the described activeconstituents of 0.5% to 20% (weight percent, down together) in pulvis, preferably its content is 1% to 10%; Contain 1% to 90% activeconstituents in wettable powder, preferably its content is 10% to 80%; Contain 1% to 90% activeconstituents in missible oil, preferably its content is 10% to 40%.
For example, for described missible oil, can will carry out uniform mixing as the The compounds of this invention of activeconstituents and solvent and tensio-active agent etc. and make, dilutable water be to prescribed concentration during use.For described wettable powder, can be with as mixing such as The compounds of this invention, solid carrier and the tensio-active agents of activeconstituents and pulverize and make, water dilutes during use.For described pulvis, can will be mixed together as the The compounds of this invention of activeconstituents and solid carrier etc., the gained mixture can directly use.Certainly, the working method of preparation never is limited to foregoing.Those skilled in the art can select suitable method according to described activeconstituents and application target etc.
Except the described compound by general formula (I) expression as activeconstituents, sterilant of the present invention, miticide or sterilant can comprise any suitable activeconstituentss such as other sterilant, miticide, sterilant, insect growth regulator(IGR), plant-growth regulator and soil improvement agent.
For the use of sterilant of the present invention, miticide or sterilant, can select the application method used always, as cauline leaf spraying, used for ponds, soil treatment and seed treatment etc.For example, when adopting the cauline leaf spraying, as activeconstituents by general formula (I) but the working concentration scope of the compound of expression is 1 to 1000ppm emulsion, suspension or wettable powder, preferably its concentration is 1 to 500ppm.
Beneficial effect of the present invention:
Novel alpha-cyano-N-benzyl pyrazole acidamide compound disclosed by the invention has good prevention effect to harmful germ, harmful insect and mite class, therefore this compound can have the good advantage of high reactivity, low consumption and security (seeing the routine data of test for details) with sterilant, miticide or the sterilant in preparation agricultural, gardening and flower culture field.In addition, this compound also can be used for preparing the pest control agent in fields such as forestry, livestock industry, warehousing and public health.Preparation method's simple possible disclosed by the invention.
Embodiment
For the ease of to further understanding of the present invention, the embodiment that provides has below done more detailed description to it.These embodiment are not to be used for limiting scope of the present invention or implementation principle for narration only.
The preparation of embodiment 1:N-(alpha-cyano-4-tertiary butyl benzyl)-4-chloro-3-ethyl-1-methylpyrazole-5-methane amide
With freshly prepd 4-chloro-3-ethyl-1-methylpyrazole-5-formyl chloride (12.0g, 0.055mol) and the solution formed of toluene (30ml), under stirring and ice-water bath cooling, slowly be added drop-wise to by alpha-cyano-4-tert-butyl benzyl amine (10.0g, 0.05mol), (6.0g is 0.06mol) and in the mixed solution formed of toluene (200ml) for triethylamine.After dropwising, reaction mixture is warmed up to about 30 ℃, and continues to stir under this temperature, chromatogram tracking to reactant transforms fully substantially, needs 4-5 hour approximately.Pour resulting reaction mixture into (300ml) in the water, standing demix.Organic layer is with saturated common salt water washing and behind anhydrous sodium sulfate drying, the decompression precipitation, and resistates is title compound (compound N is o.6 in the table 1), heavy 15g, 63～64 ℃ of fusing points.
Embodiment 2:
According to embodiment 1 described method, adopt corresponding pyrazol formyl chloride and alpha-cyano benzylamine or its hydrochlorate to synthesize described other alpha-cyano-N-benzyl pyrazole acidamide compound of preparation table 1.
Table 1
| Compound N o. | R 1 | R 2 | R 3 | R 4 | X | Fusing point (℃) |
| 1 | CH 3 | C 2H 5 | i-C 3H 7 | Cl | Cl | 155-157 |
| 2 | CH 3 | C 2H 5 | CH 3 | CH 3 | Cl | 76-78 |
| 3 | CH 3 | C 2H 5 | H | Cl | Cl | 122-124 |
| 4 | CH 3 | C 2H 5 | H | CH 3 | Cl | 110-112 |
| 5 | CH 3 | C 2H 5 | CH 3 | t-C 4H 9 | Cl | 117-119 |
| 6 | CH 3 | C 2H 5 | H | t-C 4H 9 | Cl | 63-64 |
| 7 | CH 3 | C 2H 5 | i-C 3H 7 | t-C 4H 9 | Cl | Thick |
| 8 | CH 3 | C 2H 5 | H | H | Cl | 110-112 |
| 9 | CH 3 | C 2H 5 | H | CN | Cl | 129-131 |
| 10 | CH 3 | C 2H 5 | H | t-C 4H 9 | Br | Thick |
| 11 | CH 3 | C 2H 5 | CH 3 | t-C 4H 9 | Br | 119-122 |
| 12 | CH 3 | C 2H 5 | i-C 3H 7 | t-C 4H 9 | Br | Thick |
| 13 | CH 3 | C 2H 5 | H | H | Br | 84-87 |
| 14 | CH 3 | C 2H 5 | H | H | NO 2 | Thick |
| 15 | CH 3 | C 2H 5 | H | t-C 4H 9 | NO 2 | 139-143 |
| 16 | C 2H 5 | C 2H 5 | CH 3 | t-C 4H 9 | Cl | Thick |
| 17 | C 2H 5 | C 2H 5 | CH 3 | t-C 4H 9 | Br | Thick |
| 18 | CH 3 | C 2H 5 | H | t-C 4H 9 | H | 77-79 |
To narrate below with the The compounds of this invention is the formulations of active ingredients example, and described formulation example can be used as sterilant, miticide or the sterilant in agricultural, gardening and flower culture field.But embodiments of the present invention are not limited to following content.
Example of formulations 1: wettable powder
5 parts of 20 parts of The compounds of this invention, 10 parts of white carbon blacks, 55 parts of kaolin, 10 parts of sodium laurylsulfates and calcium lignin sulphonates, the uniform mixing promoting the circulation of qi stream of going forward side by side is pulverized together, obtains activeconstituents and be 20% wettable powder.
Example of formulations 2: pulvis
93 parts of 2 parts of The compounds of this invention, 5 parts of white carbon blacks and kaolin is uniform mixing and pulverizing together, obtains activeconstituents and be 2% pulvis.
Example of formulations 3: missible oil
10 parts of The compounds of this invention are dissolved in the mixed solvent of being made up of 40 parts of dimethylbenzene and 35 parts of dimethyl formamides, add 15 parts of soil temperature 80 emulsifying agents then, stir and uniform mixing to obtain activeconstituents be 10% missible oil.
Example of formulations 4: suspension agent
The slurry of 20 parts of The compounds of this invention, 15 parts of Sodium dodecylbenzene sulfonatees, 15 parts of ethylene glycol, 1 part of xanthan gum and 49 parts of compositions of water carries out wet grinding with ball mill, obtains activeconstituents and be 20% suspension agent.
To narrate with the The compounds of this invention test example of the sterilant, miticide or the sterilant that are activeconstituents below.But embodiments of the present invention are not limited to following content.
Test example 1: to the insecticidal effect of mythimna separata
Select 3 instar larvaes, employing is soaked the leaf feeding method and is carried out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.Select diameter 90mm culture dish, cover the filter paper of one deck diameter 90mm at the bottom of the ware, with dropper add the 1ml tap water on filter paper to keep the humidity in the culture dish; The clip blade is cut into the long leaf section of 50mm to the laboratory from the maize seedling of growing about 40 days, and every ware is put into 4 leaf sections.With tweezers the leaf of Semen Maydis section was soaked for 10 seconds in soup, put back to culture dish after the leaf section behind the dipping is waited to dry.Insert 10 3 instar larvaes (each concentration triplicate) with the every ware of writing brush.Move to 25 ± 1 ℃ of observation ward after the processing, check borer population anyway behind the 72h, statistics mortality ratio (stiff with larva is death standard).
Compound N o.6, No.10, No.15 and the mortality ratio of No.18 under 1000ppm concentration be 100%.
Test example 2: to the insecticidal effect of small cabbage moth
Select 3 instar larvaes, employing is soaked the leaf feeding method and is carried out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.Choose luxuriant dish, clean and dry, make the leaf dish, in soup, soaked for 10 seconds and take out, in the culture dish for the treatment of to pack into after nature dries with punch tool.Every ware inserts 10 of 3 instar larvaes of small cabbage moth (each concentration triplicate).Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (stiff with larva is death standard).
Compound N o.6, No.10, No.15 and the mortality ratio of No.18 under 1000ppm concentration be 100%.
Test example 3: to the insecticidal effect of black bean aphid
If aphid is a subjects, adopt pickling process to carry out the insecticidal effect test with 3 ages in days.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.5 one-tenth aphids are inoculated on the high broad bean seedling of 30-50mm, remove into aphid behind the 24h, 30 left and right sides primiparity are arranged approximately on each broad bean seedling if aphid; Got 3 ages in days if aphid is cut the broad bean seedling along basal part of stem to the 3rd day, if record is the aphid radix.Tool if take out the broad bean seedling of aphid soaked for 5 seconds in soup after, is inserted in the bottle that clear water is housed (each concentration triplicate).Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (stiff with aphid is death standard).
Compound N o.6, No.10 and the mortality ratio of No.18 under 1000ppm concentration be 100%.
Test example 4: to the insecticidal effect of carmine spider mite
To become mite is subjects, adopts pickling process to carry out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made miticide respectively.With pure water resulting miticide missible oil is diluted, uniform mixing obtains the soup of desired concn.In the culture dish of diameter 90mm, put into the sponge sheet of the about 80mm of diameter, and fill with water, on sponge, put an onesize thieving paper again, the broad bean blade of making even whole, the back side is tiled on the filter paper up, receives on the broad bean blade with 20 of the one-tenth mites of writing brush picking health.Put back to (each concentration triplicate) after becoming the broad bean blade of mite in soup, to soak for 5 seconds with tweezers gripping tool.Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (is death standard to become mite stiff).
Compound N o.6, No.10, No.14, No.15 and the mortality ratio of No.18 under 1000ppm concentration be 100%.
Test example 5: to the insecticidal effect of culex pipiens pollens
Select 3 instar larvaes, adopt continuous immersion method to carry out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.Fish for 20 of 3 instar larvaes, drop into and fill in the enamel basin of soup continuous immersion liquid 72h (each concentration triplicate).Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (stiff with larva is death standard).
Compound N o.3, No.4, No.6, No10, No.14 and the mortality ratio of No.15 under 10ppm concentration be 100%.
Test example 6: to the sterilization effect (the little pot-culture method of live body) of cucumber downy mildew
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting sterilant missible oil is diluted, uniform mixing obtains the soup of desired concn.Choose the cucumber seedling of two leaves, one heart stage normal growth, soup is evenly sprayed in the Folium Cucumidis sativi surface with the air compressor control pressure.Behind the 24h, evenly spray 1 * 10 in the second true leaf back side
5The spore suspension of spore/milliliter, every 1 milliliter of leaf inoculum size (each concentration triplicate).Postvaccinal cucumber seedling is placed in the greenhouse to be cultivated, and preserves moisture, and 24 ℃ of temperature, relative humidity be greater than 95%, illumination every day 12 hours, dark 12 hours.Carry out result's investigation after 7 days.
Compound N o.1, No.3, No.4 and No.6 show good sterilization effect to bacterium of downy mildew of cucumber under 1000ppm concentration.
Test example 7: to the sterilization effect (the little pot-culture method of live body) of wheat hypochnus
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting sterilant missible oil is diluted, uniform mixing obtains the soup of desired concn.Choose the stem and leaf of Wheat of two leaves, one heart stage normal growth, soup is evenly sprayed in stem and leaf of Wheat leaf surface (each concentration triplicate) with the air compressor control pressure.Behind the 24h, with diameter 5mm mycelia piece, paste the leaf base that causes the stem and leaf of Wheat of wound through acupuncture, every alms bowl is pasted 10.Postvaccinal stem and leaf of Wheat is placed the aluminium basin, in the aluminium basin, add an amount of tap water and keep interpolation.25 ℃ of room temps, illumination every day 12 hours, dark 12 hours.Carry out result's investigation after 7 days.
Compound N o.1, No.2, No.3, No.6 and No.7 show good sterilization effect to rhizoctonia cerealis under 1000ppm concentration.
Claims (13)
1, the alpha-cyano-N-benzyl pyrazole acidamide compound of representing by general formula (I):
Wherein, R
1Expression C
1-C
5Alkyl; R
2Expression C
1-C
5Alkyl or C
1-C
5Haloalkyl; R
3Expression hydrogen or C
1-C
5Alkyl; R
4Expression hydrogen, halogen, cyano group, C
1-C
5Alkyl, C
1-C
5Alkoxyl group, C
1-C
5Haloalkyl, aryl, substituted aryl, aryloxy or substituted aryloxy; X represents hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base.
2, pyrazol acid amide compounds according to claim 1, wherein R
1The C of expression
1-C
5Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl; R
2The C of expression
1-C
5Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl or cyclopropyl; R
2The C of expression
1-C
5Haloalkyl is methyl fluoride, chloromethyl, brooethyl, difluoromethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl or 1-(trifluoromethyl) ethyl; R
3C
1-C
5Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl, 2-methyl-isobutyl or cyclopropyl; R
4The halogen of expression is fluorine, chlorine, bromine or iodine; R
4Expression C
1-C
5Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 2-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl or cyclopropyl; R
4The C of expression
1-C
5Alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy or ring propoxy-base; R
4The C of expression
1-C
5Haloalkyl is methyl fluoride, chloromethyl, brooethyl, difluoromethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl, 1-(trifluoromethyl) ethyl etc.; R
4The aryl of expression is phenyl, halogenophenyl, p-methylphenyl, o-tolyl, a tolyl or p-trifluoromethyl phenyl; R
4The aryloxy of expression is phenoxy group, halogenated phenoxy, to tolyloxy, oxy-o-cresyl, a tolyloxy or 4-(trifluoromethyl)phenoxy; The halogen that X represents is fluorine, chlorine, bromine or iodine; The C that X represents
1-C
3Alkyl is methyl, ethyl, n-propyl or sec.-propyl; The C that X represents
1-C
3Alkoxyl group is methoxyl group, oxyethyl group, positive propoxy or isopropoxy;
3, pyrazol acid amide compounds according to claim 1 and 2, the R in the general formula (I)
1Be methyl, R
2Be ethyl, R
3Be hydrogen, X is a hydrogen or halogen.
4, the preparation method of alpha-cyano-N-benzyl pyrazole acidamide compound according to claim 1, according to following reaction equation, under the situation that has alkali or alkali-free to exist, with an organic solvent under-10 to 60 ℃ of conditions, make the reaction of pyrazol formyl chloride (III) and alpha-cyano benzylamine (IV), separating (I) gets final product
Wherein, substituent R
1, R
2, R
3, R
4Identical with X with the definition in the general formula (I).
5, preparation method according to claim 4 is characterized in that organic solvent is that reaction is not had directly any inert solvent of influence, comprises aromatic hydrocarbons, ketone, halohydrocarbon, ester class or polar solvent; Described alkali comprises alkalimetal hydride, alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate or organic bases.
6, preparation method according to claim 5, it is characterized in that aromatic hydrocarbons is benzene, toluene or dimethylbenzene, ketone is an acetone, methylethylketone or mibk, halohydrocarbon is a chloroform, methylene dichloride or ethylene dichloride, the ester class is methyl acetate or ethyl acetate, polar solvent is a tetrahydrofuran (THF), acetonitrile diox, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide or pyridine, alkalimetal hydride is a sodium hydride, alkali metal hydroxide is sodium hydroxide or potassium hydroxide, alkaline carbonate is yellow soda ash or salt of wormwood, and alkali metal hydrocarbonate is sodium bicarbonate or saleratus, and organic bases is pyridine or triethylamine.
7, preparation method according to claim 4 is characterized in that temperature of reaction is 0～30 ℃.
8, preparation method according to claim 4, the method that it is characterized in that separation (I) is under the situation of using water-soluble organic solvent, decompression earlier removes organic solvent, in resistates, add water, extract described resistates with water-fast aromatic hydrocarbons, halohydrocarbon or esters solvent then, and, with anhydrous sodium sulphate or anhydrous magnesium sulfate organic phase is carried out drying again with the resulting extraction liquid of saturated common salt water washing, decompression removes organic solvent then; When using water-fast organic solvent, then in the gained reaction mixture, add water and saturated common salt water washing successively, precipitation reduces pressure after the organic phase drying; After boiling off organic solvent, can carry out purification processes to the resistates that obtains by recrystallization or column chromatography, thereby obtain compound by general formula (I) expression.
9, described according to Claim 8 preparation method is characterized in that water-fast aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and halohydrocarbon is chloroform, methylene dichloride or ethylene dichloride, and the ester class is an ethyl acetate.
10, with each described pyrazol acid amide compounds or its hydrochlorate among the claim 1-3 as the pest control agent of activeconstituents.
11, pest control agent according to claim 10 is characterized in that this pest control agent is sterilant, miticide or sterilant.
12, pest control agent according to claim 10 is characterized in that its formulation is missible oil, pulvis, wettable powder, suspension agent, granule, water-dispersible granules or aqueous emulsion.
13, pest control agent according to claim 10 is characterized in that pyrazol acid amide compounds or the content (weight percent, down together) of its hydrochlorate in pest control agent as activeconstituents is 0.1% to 99.5%; Usually, contain 0.5% to 20% described activeconstituents in pulvis, preferably its content is 1% to 10%; Contain 1% to 90% activeconstituents in wettable powder, preferably its content is 10% to 80%; Contain 1% to 90% activeconstituents in missible oil, preferably its content is 10% to 40%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012059048A1 (en) | 2010-11-03 | 2012-05-10 | 中国中化股份有限公司 | Pyrazole amide compound and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012059048A1 (en) | 2010-11-03 | 2012-05-10 | 中国中化股份有限公司 | Pyrazole amide compound and use thereof |
| CN102464618A (en) * | 2010-11-03 | 2012-05-23 | 中国中化股份有限公司 | Pyrazolecarboxamide compound and application thereof |
| US8614214B2 (en) | 2010-11-03 | 2013-12-24 | Sinochem Corporation | Pyrazole amide compounds and uses thereof |
| CN102464618B (en) * | 2010-11-03 | 2014-07-23 | 中国中化股份有限公司 | Pyrazolecarboxamide compound and application thereof |
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